Vibrational predissociation from different asymmetric rotor levels: full dimensional quantum dynamics for ArI2 with total angular momentum J = 10

Using the accurate global potential energy surfaces for the 11A′′ and 21A′ states reported in the previous sister Paper I, detailed quantum dynamics calculations are performed for these adiabatic surfaces separately for J = 0 (J: total angular momentum quantum number). In addition to the significant overall contributions of these states to the title reactions reported in the second Paper II of this series, quantum dynamics on these excited potential energy surfaces (PES) are clarified in terms of the PES topographies, which are quite different from that of the ground PES. The reaction mechanisms are found to be strongly selective and nicely explained as vibrationally nonadiabatic transitions in the vicinity of potential ridge.

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CHEMICAL REACTIONS IN THE O(1D) + HCl SYSTEM II.

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633602000208 ◽

2002 ◽

Vol 01 (02) ◽

pp. 275-284 ◽

Cited By ~ 11

Author(s):

HIDEYUKI KAMISAKA ◽

HIROKI NAKAMURA ◽

SHINKOH NANBU ◽

MUTSUMI AOYAGI ◽

WENSHENG BIAN ◽

...

Keyword(s):

Angular Momentum ◽

Potential Energy ◽

Potential Energy Surfaces ◽

Quantum Dynamics ◽

Total Angular Momentum ◽

Branching Ratio ◽

Reaction Dynamics ◽

The Third ◽

Angular Momentum Quantum Number ◽

Energy Surfaces

Using the accurate global potential energy surfaces for the 11A′, 11A′′, and 21A′ states reported in the previous sister Paper I, detailed quantum dynamics calculations are performed for these three adiabatic surfaces separately for J = 0 (J: total angular momentum quantum number). Overall reaction probabilities for O + HCl → OH + Cl and H + ClO, the branching ratio between the two reactions, effects of the initial rovibrational excitation, and product rovibrational distributions are evaluated in the total energy region E tot ≤ 0.9 eV. Significant contributions to the overall reaction dynamics are found from the two excited 11A′′ and 21A′ potential energy surfaces, clearly indicating the insufficiency of the dynamics only on the ground 11A′ surface. The detailed dynamics on the excited surfaces are reported in the third paper of this series.

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Total angular momentum and decay of unimolecular resonances IVR-mediated vibrational predissociation

Journal of the Chemical Society Faraday Transactions ◽

10.1039/a606041b ◽

1997 ◽

Vol 93 (5) ◽

pp. 909-918 ◽

Cited By ~ 19

Author(s):

Evelyn M. Goldfield ◽

Stephen K. Gray

Keyword(s):

Angular Momentum ◽

Total Angular Momentum ◽

Vibrational Predissociation

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QUANTUM DYNAMICAL CALCULATION OF ALL ROVIBRATIONAL STATES OF HO2 FOR TOTAL ANGULAR MOMENTUM J = 0–10

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633610005815 ◽

2010 ◽

Vol 09 (02) ◽

pp. 435-469 ◽

Cited By ~ 14

Author(s):

WENWU CHEN ◽

BILL POIRIER

Keyword(s):

Angular Momentum ◽

Quantum Dynamics ◽

Bound States ◽

Total Angular Momentum ◽

Energy Levels ◽

Rigid Rotor ◽

Spectral Transform ◽

Software Modules ◽

Rovibrational States ◽

Rotor Model

The energy levels and wavefunctions for all rovibrational bound states of HO2 are systematically computed, for all total angular momentum values J = 0–10. The calculations are performed using ScalIT, a suite of software modules designed to enable quantum dynamics and related calculations to be performed on massively parallel computing architectures. This is the first-ever application of ScalIT to a real (and very challenging) molecular application. The codes, and in particular, the algorithms (optimal separable basis, preconditioned inexact spectral transform, phase space optimized discrete variable representation basis) are so efficient that in fact, the entire calculation can be performed on a single CPU — although parallel scalability over a small number of CPUs is also evaluated, and found to be essentially perfect in this regime. For the lowest 11 vibrational states, the rotational levels for J = 0–10 fit fairly well to a rigid rotor model, with all vibrational-state-dependent rotational constants, B eff (v), close to values obtained from a previous calculation for J = 0 and 1 [J Chem Phys107:2705, 1997]. However, comparatively larger discrepancies with the rigid-rotor model are found at the higher J values, manifesting in the observed K-splitting (along the O–O bond) of rovibrational levels. This supports earlier work [J Chem Phys113:11055, 2000] suggesting that Coriolis coupling is quite important for this system.

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